Chaev siccatives



Patented July 24, 1951 ALIPHATIGUNSATURAYEEU; BRANCHED srcca'rlvns wiilimt'n. m Berkeley, and Zephaniah H.

Ballmer, J'r., Lafayette, 0

fornia Re Calif a corporation of search- Corpor'atlon; San Francisco.

Delaware allt.,.asslznors to. Cali- Nonrawfnz'a Appllcatlolr-Ilfly 0,1948,

. sci-almanac This invention relates varnishes, lacquers, oil: colors; Writing and -print ingl inks, and plastic masses-which contahi drying oils and more particularly, to novel polyvalent metal-ldri'ers prepared-from"condensation prod-I ucts derived from unsaturated, branched-chain polymeric picnics, and, alpha-beta unsaturated aliphaticacids andltocompositionsofl matter prepared therefrom, and to the processes for their preparation; 1 l l In recent years the: prior art'ofi paintindustry has evolved to the point Wherdinstead iof cool:- ing metallic compounds, such. as cobalt oxide-:01 carbonate, with linseed: oil with'an attendantflre hazard, it prefers to add liquid drlers to'a drying; oil (frequently containing pigments); thereby avoiding use or any heat and, consequently, all firehazards. And by liquid'driers wememi polyvalent metal salts of oil-soluble carboxyllc' acids dissolved in a thinner, which solutionlis de sirably compatible with drying oils andwhich ac;- celerates the drying time of said drying oil. Thus, for example, the saturated'cycloparafllnic' carboxylic acids otherwise known as naphthenic acids, have been previously used in: liquiddrier compositions in theiormof their metallic salts.

The problem of incorporating. sumcient' amounts; of polyvalenti metal drier intotthlnner solvents, which solvents are-compatible-wltlr drying oils, has-beenavexatious one in the paint ini dustry. when the polyvalent metalsaltsof high molecular weight straightchain, saturated or. unsaturated carboxylicacids are used, they general- 1y do not dissolvein thinner solvent sufiicientl y well to yield liquid driers'of a desirable 6 per cent metal content. Inthe few cases wherefi per cent metal content is obtainable with the: said high molecular weightstraight chain carboxyJic-acids; the solubility characteristics of the concentrated solution are such that the liquid drier gels on standing. This gelation frequently is so Bad as to produce a hardlmass in the container and; obviously such driers are no longer-liquid and are therefore extremely ditficult, if not-impossible ad'- ditions toa drying oil. i p

The production; of liquid driers-of 6 per cent al, more metal. content is highly desirable foneaserof handling and to avoid: the additionot excessive amounts of undesirablethinner to the dryings'oill In normal practice; using such a highly-colleen trated liquid drier solution, the useofi aboutfic'c':

. of, drier per quart of dryingoil or paintproduct is sufficient.

It is therefore readily seen that conceritrateti to driers 'or siccatives for liquid driers arehighly desirable invthe artl Ali? 55 tempts to attain such high concentrations using na htiienic aciddriers, necessitate the use of excess fieenaphthenic acid since the neutral metal naphthenatesfl are unstable and gel on aging, with a consequent increase of viscosity. The amount of excess acid required to prevent such gelation amounts toaboutlo to 15 per centover and above the amountrequired to neutralize the metal used lntlie preparationof the metal naphthenate drier. Such an excess of acid is disadvantageous for the rateof. the subsequently compounded drying; oilas well: as being bad for the durability of tlicgpaintfilm land this excess acid may even react with the-pigmen in the" case of pigmented.drying oil-compositions, to cause'liv'ering and gelati'onl therein. a

, It'is thus'seen thata suitable liquid drier reqllires oompatability with drying oils, with or without pigments, and freedom from formation of curd-ling or gelationin the ultimate diyingoillcomposition-s This compatibility of the liquididrieriinthe drying oil medium is of course desired; over and. above. the question of compatibilitypffthe metallic-drienperse-in its liquid drier solventlthinner). medium. a

, Thus it is readily understood th'atthe prepara ibi'r ofa drier having the foregoing combination ofdesirable properties is not generally capable of prediction, with theresult that compounding 1 s,; to this day, considered an art-and not a predictable science. .f It? an object. of. this inventionto prepare newandi useful synthetically prepared carboxylatemetallicdriershaving a branched-chain unsaturated! olefinic polymeric structure-as an essential constituentthereof.

Itisialso an-objectof this-invention to prepare a new classlot metal carboxylate driers in dry, or more preferably, in solution form andcapable 'of economical preparation and suitable forxuse in on uch modernpaints as those comprising various synthetic organic materials, such the various alkyd resins, the various ureaforriialdehyderesins; the numerous phenol-formaldehyde resins,. and the like; u

Stilt another objector this'invention is to obrelatively low molecular weight olefinic polyyalent drier metal salts having a.- branched structure whichshow good solubility in liquid-thinner type solvents, such as naphtha, Stoddard solvent, and the like, in order to prepare liquidldrier compositions of high polyvalent drier metal content.

Still another object of this invention: is to,

produce novel non-acidic drier salts which, at

. high concentration in lquid thinner solvent, will ner solvent compatibility, andi'otheif valuable ple, are excellent paint driers of exceptionally 2,561,781 3 4 I olefins used in our invention, we employ such olefins as ethylene, propylene, butylene, and the like, under such operating conditions of temperature, pressure, reaction velocity, catalyst, and ""te f r; 5 fthegi ike cdndi tions readily obtainable in the prior art) as to yield the desirable highly branched-chain polymeric olefins. Thus propene-l, when polymerized by these well-known emethods yields substantial amounts of. side lchainibranching in its various polymeric unsaturated forms, such, for example, as in its trimers, body of the disclosure. A tetramers, and the like. Likewise butene-l, poly- We have discoveredthatdrier meta Sn e' iiedibrwel kn p r a t t od yi l s certain synthetically prepared unsaturated .acids liqlyrners also containing substantial which acids are prepared by condensation of' 1 in amounts of side chains and having an unsatumers of low molecular weight .ol'efin s chin-ratedstructure. ethyl ne, propylene, butylene, and the likef with "The branched-chain structures present in our an alpha-beta unsaturated aliphatic acid, sugh polymers persist, possibly w1th some isomerizaas crotonic acid, are excellent driers for drying ti'oflfiifdur fi metal dller Salts, e after oils and, furthermore, we have discovered that condensation with alpha-beta unsaturated carthey exhibit excellent co1or,linsfedoi1 an -i515; boxyu acids. Furthermore, these slde chains, associatdwith'an unsaturated bond, apparently properties desired in a paint drierj for end *a combination of valuable properties to our x mple, we found that wh n pf 'pylh mr polyvalent metal drier salts; such properties as is condensed with crotonic acid tlireisobt net highiisglupflity in thitmer solvents t a highly branched-chain nonenyl' ,buty'ri d use of extraneous acid, excellent compatibility whose cobalt soaps, also mereiy by Of with thinner solvents with avoidance of .curdling,

' stringiness-and insoluble residues in said thingood color, odor and oil, as we'll as thinner s 1- I ne'r'solvents even after prolonged standing, along vent, compatibility. i 0 with equally excellent compatibility with drying We have, moreover, discovered that in' general n p m e p p any olefin polymer of abouto to 20 a 5a :For purposes-0f clarifying the preparation of and possessing a highly an h h g our unsaturated branched-chain polymers and ture, along with an unsaturated d fifi m I merely-by way of llustrat on, we'haveexemplified is suitable for the condensation withanaipiia thepreparatmofwr metal'pamt drlersm data beta unsaturated aliphatic acid, and"'that the starting from a p unbranched. Olefin a obtains as a reaction productan unsaturated endingYwithiheideslredpllylelent'metal. t branched-chain-carboxyli id'tt v l if Itisto be understood that equivalent variations metallic salts constitutet u I as to; temperature, pressure, feed rates, catalysts, tion. The olefin polymer of 6m. 'ihvefitmfiife 4 and similarvariablequantitiesare also a part of prepared from normally gaseous'olefins'r'suchas our invention! I ethylene, propylene, butylene, and then well-known polymerization pr'oeesse'sjfi; 1 class of acids we usei's exemplified by crotonic acid, but alpha-beta unsaturated acids of inb'mfg '45 bregn te with 75% phosphoric acid' were placed to about 8 carbon atomsare dui tesatisfactory in a rtical steel 'tube surrounded by a heating in the preparation of our condensed br anfi-d; iac t.'['riie'cata1yst was heated to 200 C. and chain unsaturated carboxylic acidswhichw find braiby ene was; ied downward through the catauseful as a source material fo'r'the preparation l i i f of t gauge of our metallic driers. By wa of example iilu i ressure of300' pounds per square inch. The protrating the range of equivalentsfwe find that pylenlpolymeri'zed, and-the polymers plus unretrior di-isobutylen'e may be used in lieu of i fi t yle ewe Withdrawn from the tt polypropylene trimer, and that angelic ay ofthe' catalyst chamber at a rate suchv as to mainbe substituted for the preferred crotonic alt tain theinternalgauge pressure at 300 pounds ive entirely satisfactory branche d-chainblefini'c squa Th' reaction product was stabicarboxylic acid condensates useful in the pre s- 11sec, deoolorized, by percolation through fullers give a free-flowing liquid drier, devoid of a tendency to body or to form a gel, or to become cloudy or stringy on storage. It is also 'an object of this}.in]ventio' h pare a metallic paint drier that yields "a'cl'ear, non-curdled, non-stringy and homogeneous solu; tion when mixed with thinner, such as Stoddard solvent, or a base oil, such as linseed-or oiticica; oil, and the like. 1 Other objects will become apparent flQlf'l the .E ramplaL-el-Prepamtion ofproilwl ene trimer tionfmo stly nonenes, boiled between 104 C. and

The metallic salts, i. e.,' soaps,'preparedfrom i t 1-65%C;3,nd nad' bromine numberof l26.

our acid condensation product's by'r'eaction w h the commonly used polyvalent drier metal" pounds such as, for example, the oxides, sulfates, carbonates, etc. of cobalt, ieeu:'ineneanese,*eai: cium, zinc, iron; and the like, have'the property Of b ng completely compatible witli'p th ii sealed a steel vessel. The mixture was heated ners, such as Stoddard solvent and the like, to 200 C. for 5 hours, cooled, and iractionally disgive clear, homogeneous, non-stri'rie'yv fi 'iiontilled. The unreacted material was removed at curdling liquid driers or high drier met'ai an": atmosphe icp e f s r run. The desirable centration and low viscosity, evenbnsubs'equent storage of prolonged duration. This surprising nd r ed o d pressure y distillation p, 170 and highly useful combination of prdpertis'we 7'0 C Jat'50'mm. Hg.:pressure; The fraction containattribute to the highly branched-chain structure ifig f fi nylb yrio acid was separated from re together with the unsaturation characteristics sidualcrotonic'acid by water washings and from present in our driers and associated withth re id l p y $r Olefins y extraction with polymeric nature of our carboxylate'siaustic soda. [Then'onenyl butyric acid is ob.-,

In the polymerization of the'normally gaseous; tained' treating the sodium salt with a stoichio 6.3 mols' of 'the' trimer prepared according to condensate offnonenylbutyric acid was removed it apatalyst consisting offcharcoal imration of ourpolyvalent ta i ga I earth and fractionally distilled. The trimer frac- EiampleI-ZQPreparation of nonenyl butyric acid Example- 1" and 3.0 mols of crotonic acid were Calculated "Found.

Per cent carbon 73.8

Example 3.-Preparation of cobaltnjoncny'l butyrate 9.5 grams of nonenyl butyric acidwere neutralized with a dilute solution of sodium hydroxide to form an aqueous solution of the sodium soap. An excess amount of cobalt sulfate was added to the soap solution and the cobalt nonenyl butyrate formed immediately, as an insoluble material. The cobalt soap was extractedlfrom this aqueous solution by means of Stoddard solvent. The solvent extract was then evaporated until the concentration of cobalt metal was about 5.8%. At this concentration, the drier was completely compatible with the Stoddard thinner and exhibited a desirable low viscosity as shown by the following properties:

Color Deep violet Clarity Clear Residueunl -4 None Viscosity A-3 Gellation in solution None visible Gardner-Holdt.

It is thus apparent that the drier salt of our acid condensation product yields a liquid.- drier of high concentration without residue and without gellation, and of low viscosity and excellent clarity.

One part by volume of this concentrated drier solution of Example 3 was added to 19 parts by volume of linseed oil and the mixture was thoroughly shaken, resulting in a clear, homogeneous solution. No curdling, stringing or formation of insoluble residue occurred, thereby indicating complete compatibility between our novel liquid drier and linseed oil.

It will be seen from Example 3 supra that the compatibility of our novel driers with linseed oil, the most commonly used base oil, is such as to yield clear, homogeneous solutions exhibiting neither curdling nor stringing nor formation of insoluble residue, in contrast to presence of such disadvantages frequently present in driers prepared from high molecular weight fatty acids and oxidized parafhns.

Fiu'thermore, we have found that our polyvalent metal liquid driers, while preferably used at about 6 per cent metal concentration, particularly with respect to cobalt metal, may nevertheless be used at a concentration greater than 6 per cent metal without gel formation. Thus concentrations of up to about 8 per cent metal cobalt in the cobalt liquid driers of our invention are feasible and concentration as low as 0.1 per cent are useful for special purposes. Similar concentrations of other polyvalent metals of our drier acids are likewise free of gelation.

Aside from the valuable properties enumerated above, we have also discovered that the metal driers of our invention are per se very valuable driers, comparable in drying power to such cobalt driers as those obtainable from Z-ethyl hexoic, fencholic or naphthenic acid as more fully presented in the following example:

' Gardner-Holdt).

8, Example 4.-Drying action of cobalt nonenyl .butyrate The following vehicle formulations were prepared by adding liquid drier. The lead naphthenateliquid drier contained 24% lead metal. The cobalt liquid driers contained about 6% cobalt metal in the case of both cobalt nonenyl butyrateand cobalt naphthenates; the latter containing excess naphthenic acid as previously mentioned.

F O RM'ULATIO N Vehicle A Vehicle B Vehicle 0 Drier Formulation 1:

. Ieadnaphtlienate 0.6% Pb... 0.6% P

cobalt nephthenate 0. 0.03% (30;. Drier Eormulationzz lead naphthenatein 0.6% Pb 0.6% Pb..-

' cobalt nonenyl butyrate.. 0.03% C 0.03%Co.. Formulation-3: cobalt naph-= 0.03% 00..

thenate'. Formulation 4: cobalt nonenyl 0.03% 00.. i

butyrste. i

Set to Dust Tack Touch Free Free Vehicle A (films 0.001 thick): Hours Hours Hours Drier formulation 1 4 5 Drier formulation 2 .l 3 4 5 Vehicle B (films 0.0015" thick):

Drier formulation 1 2 2. 5 3 Drier formulation 2... 2 2. .5 3 Drier formulation 3..- 1. 5 2 4 Drier formulation 4 l. 5 2 4 Vehicle G-Drier formulation 3 4 6 12 Vehicle C-Drier formulation 4 4 6 12 It is apparent from the above drying times that the drying action of cobalt nonenyl butyrate is comparable to that of acid-containing cobalt naphthenate and that the said cobalt nonenyl butyrate is compatible with various drying oils or drying oil containing vehicles. Thus the highly branched-chain unsaturated metal driers of our invention yield the much desired combina 'tion of high concentration of metal in thinner type solvents with a desirable low viscosity (A-3,

Our liquid driers are, furthermore, completely compatible with drying oils and are excellent driers per se.

While we have exemplified the compatibility of our cobalt driers, prepared from olefin polymers and alpha-beta unsaturated acids, with lead naphthenate and an equal weight mixture of cobalt naphthenate admixed with lead naphthenate in such vehicles as linseed oil and soybean oil alkyd, nevertheless, other oils such as dehydrated castor oil, tung oil, and the like and other alkyd mixtures are also applicable. Furthermore, while we have illustrated our invention by way of a few specific examples, nevertheless, various combinations of olefin equivalents and crotonic acid equivalents, as well as polyvalent metal equivalents, are deemed to be within the scope of our invention as more fully defined in the appended claims.

thinner and from 0.1 to about 8% of a polyvalent metal in the form of a salt acyclic ,monmolefin polymer-substituted alpha, beta unsaturated aliphatic carboxylic acid wherein ,the acyclic mono-olefin polymer substituent has a branched chain structure of 6 to 20 carbon atoms, said alpha, beta unsaturated aliphatic carboxylic acid having from 3 to 8 carbon atoms prior to said substitution, said solution being characterized by its compatibility with drying oils and stability against gelation on storage.

2. A liquid drier composition, as defined in claim 1, wherein said polyvalent metal is cobalt, said acyclic mono-olefin polymer substituent is a propylene polymer having a branched-chain structure of 9 carbon atoms and said alpha-beta unsaturated carboxylic acid is crotonic acid.

3. As a new siccative' compatible with drying oils, a polyvalent metal salt of an acyclic monoolefin polymer-substituted alpha, beta unsaturated aliphatic carboxylic acid, said acid having not more than about 8 carbon atoms prior to said substitution, and its acyclic mono-olefin polymer substituent containing from 6 to 20 carbon atoms. r I

4. As a new siccative compatible with drying oils, a polyvalent metal salt of an acyclic monoolefin polymer-substituted alpha, beta unsaturated aliphatic carboxylic acid, saidacid having not more than 8 carbon atoms prior to said substitution, and its acyclic mono-olefin polymer substituent having a branched chain structure of 6 to 20 carbon atoms.

5, As a new siccative'compatible with drying oils, a divalent metal salt of an acyclic monoolefin polymer-substituted alpha, beta unsaturated aliphatic carboxylic acid, said acid having 5 not more than 8 carbon atoms prior to said substitution, and its acyclic mono-olefin polymer substituent having a branched chain structure of 6 to 20 carbon atoms.

6. As a new siccative compatible with drying 10 oils, a polyvalent'metal salt of an acyclic monoolefin polymer-substituted alpha, beta unsaturated aliphatic carboxylic acid, said acid having from 3 to 8 carbon atoms prior to said substitution, and its acyclic mono-olefin polymer substituent having a branched chain structure of 6to 20 carbon atoms and being a polymer of a normally gaseous acyclic mono-olefin.

7. As a new siccative compatible with drying oils, a cobalt salt of an acyclic propylene polymersubstituted crotonic acid, its propylene polymer substituent having a branched chain structure of 9 carbon atoms.

WILLIAM E. ELWELL. ZEPHANIAH H. BAILMER, JR. REFERENCES cI'rEn The following references are of record in th file of this patent: 

1. AS A NEW LIQUID DRIER COMPOSITION, A SOLUTION CONSISTING ESSENTIALLY OF A VOLATILE HYDROCARBON THINNER AND FROM 0.1 TO ABOUT 8% OF A POLYVALENT METAL IN THE FORM OF A SALT ACYCLIC MONO-OLEFIN POLYMER-SUBSTITUTED ALPHA, BETA UNSATURATED ALIPHATIC CARBOXYLIC ACID WHEREIN THE ACYCLIC MONO-OLEFIN POLYMER SUBSTITUENT HAS A BRANCHEDCHAIN STRUCTURE OF 6 TO 20 CARBON ATOMS, SAID ALPHA, BETA UNSATURATED ALIPHATIC CARBOXYLIC ACID HAVING FROM 3 TO 8 CARBON ATOMS PRIOR TO SAID SUBSTITUTION, SAID SOLUTION BEING CHARACTERIZED BY ITS COMPATIBILITY WITH DRYING OILS AND STABILITY AGAINST GELATION ON STORAGE. 